Repelience of insects



Patented Oct. 23, 1951 REPELLENCE OF' INSECTS Carolyn E. Tissol,Minneapolis, Minn., and Lyle D. Godhue, Bartlesvillc, 0kla., assignorsto Phillips Petroleum Company, a corporation of Delaware N 0 Drawing.Application October 23, 1950, Serial No. 191,728

Claims. 1

This invention relates to methods and compositions for repellinginsects. In a more specific aspect this invention relates to repellenceof roaches and flies.

Roaches and flies are troublesome pests in homes, restaurants, grocerystores, and the like. The control of these pests by the use of ordinaryinsecticides is diflicult because such materials have been found to bepartially or entirely ineffective against them. Our invention isconcerned with new and novel roach and fly repellents, and a method fortheir utilization in ridding these pests from. surfaces otherwisefrequented by them.

An object of our invention is to provide for the repellence of insects.

Another object of our invention is to provide new methods for repellingroaches and flies from surfaces otherwise frequented by them. Anotherobject is to provide highly effective roach and fly repellentcompositions. Another object is to provide a relatively inexpensivesource of roach and fly repellent materials. Other objects andadvantages will be apparent to those skilled in the art from theaccompanying discussion and disclosure.

We have now discovered that 2,3,4,5-bis(A butenylene) tetrahydrofurfuraland derivatives thereof are effective agents for repelling roaches andflies from surfaces frequented by them, when applied to such a surfacein any suitable form, such as a solution, dust, emulsion, aerosol, fog,or the like, or as a pure compound or a concentrate thereof. By way ofexample, we have found that it is convenient to dissolve 2,3,45- bis(A'-butenylene) tetrahydrofurfural in a solvent, or otherwise employ it ina suitable carrier and, apply the composition so formed. Solvents orcarriers which we have found applicable. to:

the present invention include those which are substantially inert withrespect to the active repellent ingredient. Among those materials whichare useful for this purpose are petrolatum, liquid polybutadiene,deodorized kerosene, naphthas, and other liquid hydrocarbons boilingpreferably above atmospheric temperatures. Solid inert carrier materialsare utilized, such as for example, talc, kieselguhr, and other inertcarriers which may be used in preparing dusts. The active repellentingredient of our invention may I be applied in the form of an aqueousemulsion,

preferably when employing a wetting agent, as for example, Span 20(sorbitan monolaurate), Triton X100 (alkylated aryl polyether alcohol),Tween 20 (sorbitan monolaurate polyoxyethyl-ene derivative), and others.

When employing the active repellent ingredient in a solvent or carrier,the lower effective limit of the ingredient concentration is about 0.5per cent by weight. Similarly, when employing dusts, a concentration ofthe active ingredient is preferably within the limits of 1 to 20 weightper cent. However, there is no upper limit to the concentration that canbe employed, except that dictated by economy. If desired, concentrationsof the ingredient higher than 20 per cent can be utilized in anyproportions, even as high as per cent or higher. In some instances theactive ingredient can be advantageously applied as the pure compoundwithout a carrier of any kind, or in the form of a concentrate generallyobtained during a specific preparation procedure described hereafter,wherein the material is pro-- applied will be determined by the methodof" application. Generally, when a liquid composition is sprayed onthesurface to be treated, about 0.4 to 10 grams of the active ingredientper square feet of surface is advantageously applied. Larger or smalleramounts can be applied as desired.

The 2,3,4,5-bis(A -butenylene) -tetrahydrofurfural' used as thepreferredactive repellent mate-' rial of the present invention is anearly water white liquid having a boiling point of. 53% to. 550 F.corrected. One method for the production of 2,3,4,5'-bis(A -butenylene)-tetrahydrofurrf-ural comprises the inter-reaction oft" l,.3-buta-=diene with furfural' at a temperature of from 200 F. to 300 F. for from5 to 100. hours under sufiicient pressure to maintain the reactants inliquid phase. This and other suitable conditions and methods for makingthe compound are disclosed in the copending application of J. C. Hillyerand D. A. Nicewander, Serial No. 81,413, filed March 14, 1949. Reactionof a diolefin such as 1,3-butadiene and its immediate homologues with afurfural such as furfural itself and its immediate homologues producespolycyclic reaction products of varied constitution, which includematerials which may broadly be referred to as butadiene-furfuralcopolymers. There can be isolated from the complex reaction products acompound having the probable formula 2,3, 1,5- bis(A butenylene)tetrahydrofurfural, being represented by the probable structuralformula:

Fractions obtained by fractional distillation of furfural-butadienereaction products, which fractions are composed of polycyclic reactionproducts including at least some 2,3,4,5-bis(Abutenylene)-tetrahydrofurfural, exhibit satisfactory roach repellentaction in accordance with the present invention. Thus, the 2,3,4,5-bis(Abutenylene)-tetrahydrofurfural known to be an active ingredient need notnecessarily be separated in its pure form prior to use. In addition to1,3-butadiene and furfural as starting reactants, methyl derivativesthereof wherein not more than two carbon atoms of either the butadieneor the furfural has had a hydrogen atom replaced by a methyl group canbe used to form the corresponding derivatives of 2,3,4,5-bis(Abutenylene)-tetrahydrofurfural which are employed in accordance with thepresent invention. Furthermore, chloroprene (2-chloro-l,3-butadiene),1-chloro-l,3-butadiene, and methyl-substituted derivatives thereofwherein not more than one carbon atom has had a hydrogen atom replacedby a methyl group can be reacted with a furfural of the class describedto produce the corresponding chlorine-containing derivatives of 2,3,4,5bis(A butenylene) tetrahydrofurfural which exhibit high roach and flyrepellent activity. Thus, the butadiene starting material is defined bythe structural formula:

Hiiii;

where each R is hydrogen, methyl, or chloro and at least two Rs arehydrogen. The furfural starting material is defined by the formula:

where each R is hydrogen or methyl and at least one R is hydrogen. Themost commonly used reactants are 1,3-butadiene and furfural, isopreneand furfural, piperylene and furfural, chloroprene and furfural, andeach of these diolefins with methyl furfural. All of these active roachrepellent materials will be described generically herein by the term a2,3,4,5-bis(A butenylene) -tetrahydrofurfural, and are repre sented bythe formula:

wherein R is selected from the group consisting of hydrogen and methyl,Rm is selected from the group consisting of hydrogen, methyl, andchloro, Rn is selected from the group consisting of hydrogen, methyl,and chloro, at least one R is hydrogen, at least two R'ms are hydrogen,and at least two R'ns are hydrogen.

Our invention is advantageously applied to repelling the roach speciesGerman cockroach, Blatella germam'ca (Linn), American cockroach,Periplaneta americana (Linn), Oriental cockroach, Blatta orientalis(Linn), and brownbanded cockroach, Supella supellectz'lium (Serville).These specices of roaches are common household pests and frequent onlyartificial or man made surfaces, as for example, floors, cupboards, andwall crevices associated with domestic units, hospitals, restaurants,grocery stores, and the like. These species of roaches do not frequentplant surfaces.

The advantages of this invention are illustrated in the followingexamples. The reactants and their proportions and their specificingredients are presented as being typical and should not be construedto limit the invention unduly.

The following are examples of roach repellent compositions madeaccording to our inven-- tion:

Example 1 3 Parts 2,3,4,5 bis(A butenylene) tetrahydrofurfural 5Deodorized kerosene Example 2 3 Parts An aerosol composed of 2,3,4,5bis(A butenylene)-tetrahydrofurfural 10 Freon (a mixture of 45 parts ofFreon 11 with 45 parts Freon 12 90 1 Freon 11 (trichlorofluoromethane).Freon 12 (dichlorodifluoromethane).

Triton X- wetting age 5 (alkylated aryl poly ether alcohol) Water a Byweight.

The following examples will serve to illustrate the effectiveness of thecompositions of our invention:

Example Twenty-five cc. of the composition of Example 3 was sprayed onthe floor and other surfaces in one of two adjoining darkened rooms eachbadly infested with roaches, while the other darkened room was leftuntreated. The test was conducted for a period of eight weeks, duringthe last two to three days of which roaches were observed to beinitially returning to the treated room. The untreated room, however,was regularly frequented by the pests during the entire eight weekperiod.

Example 6 Laboratory starvation tests were made which vividlydemonstrate the effectiveness of our repellents. These tests wereconducted in the following manner:

Five American roaches Periplaneta americana, provided with only water,were starved for a period of seven days and then placed in a cage with apellet (approximate cube /2 inch on a side) of a commercial dog foodpreparation. The pellet had been impregnated with 0.1 gram of 2,3,4,5bishl butenylene) tetrahydrofurfural dissolved in a small quantity ofacetone, after which the acetone was completely removed from the pelletby evaporation.

The roaches entirely avoided the food for five days, and no detectableamounts of the food were eaten at the end of seven days. From the eighthto the tenth day the roaches ate extremely small amounts from thepellet.

Example 7 Two identical shelters made from pint cardboard cartons wereplaced in an inverted position in a wire cage 18 x X 9 inches. Thecartons had a notch cut in the rim to permit roaches to enter. Food andwater were provided within the wire cage.

Five cc. of a one per cent acetone solution of 2.3.4.5 bis(A butenylene)tetrahydrofurfural was placed in one carton. The carton was revolveduntil the solution coated the entire inner surface thereof. The acetonewas then allowed to evaporate completely. The other carton wasuntreated.

Ten young adult roaches were placed in the cage in a lighted room, andall sought shelter in the untreated carton. The roaches completelyavoided the treated carton for four days.

Example 8 In accordance with the Sandwich Bait Method described by L. B.Kilgore in Soap, June 1949, several 1 x 4 inch strips of cardboard werecoated with a smooth thin film of unsulfured molasses leaving anuncoated margin about inch on all four sides. The prepared cardboardstrips were then oven-dried at 45 C.

Highly porous paper strips, cut from cushion sheets used in mimeographstencils, were impregnated with 2,3,=l,5-bis (M-butenylene)-tetrahydrofurfural, in varied amounts. Impregnation of the porousstrips was effected by immersing them in an acetone solution of the2,3,4,5- bis (N-butenylene) -tetrahydrofurfural, and then allowing thestrip to dry over a period of from 4 to 6 hours. The impregnated stripswere the same size as the baited cardboards. An impregcardboard andfastened in place by stapling. The loose fiber construction of theimpregnated paper permits the fly to remove the molasses through it.

The prepared strips, i. e., the sandwich bait,

were then exposed to house flies (Musca domestica), over 5 days old,which had been starved for 6 hours. Counts of the number of fliesfeeding on the strips were taken periodically for 2 hours. Anon-repellant material in the sandwich bait becomes black with fliessoon after being exposed and the bait will often be entirely consumed in5 minutes.

- The results of the tests of 2,3,4,5-bis(A-butenylene-tetrahydrofurfural as a fly repellent in accordance with themethod described above are tabulated as follows:

Number of Flies Feeding Oonc., per cent 1 wherein R is selected from thegroup consisting of hydrogen and methyl, Rm is selected from 'the groupconsisting of hydrogen, methyl, and chloro, Rn is selected from thegroup consisting of hydrogen, methyl, and chloro, at least one R ishydrogen, at least two Rms are hydrogen, and at least two R'ns arehydrogen.

2. A method for rendering a surface roach repellent, comprising applyingthereto a 23,4,5- bis N-butenylene) -tetrahydrofurfural associated witha carrier in an amount of at least 1 per cent by weight.

3. A method for rendering a surface roach repellent, comprising2,3,4,5-bis A -butenylene) tetrahydrofurfural thereto.

4. The method of claim 2 wherein said 2,3,45- bis n -butenylene)-tetrahydrofurfural is dissolved in a hydrocarbon solvent in aproportion of at least 1 per cent by weight.

5. The method of claim 2 wherein said 2,3,4,5- bis(A-butenylene)-tetrahydrofurfural is in an aqueous emulsion.

6. The method of claim 2 wherein said 2,3,45-

. 7- bisf'A -butenyleneltetrahydrofurfural is associated with a finelydivided solid material, as a dust.

7 A method for rendering a surface roach repellent that is otherwisefrequented by roaches, comprising applying thereto a polycyclic reactionproduct of a 1,3-butadiene compound with a furfural containing a2,3,4,5-bis(A -butenylene) tetrahydrofurfural.

8. A method for repelling roaches from a surface otherwise frequented bythem, said roaches consisting of at least one of the species Germancockroach, Blatella germanica (Linn), American cockroach, Periplanetaamerz'cana. (Linn), Oriental cockroach, Blatta orientalis (Linn),andbrown-banded cockroach, Supella supellectilium (Serville) said methodcomprising applying to such a surface only sufilcient 2,3, 1,53- bis(A-buteny1ene) -tetrahydrofurfura1 to render said surface repellent tosuch roaches.

9. The method of, claim 8 wherein said 2,3,45- bis (n -butenylene)-tetrahydrofurfural is applied to said surface admixed in aconcentration of at least one per cent by weight in a carrier, and in anamount of from 0.4 to 10 grams per 100 square feet of said surface.

10. A method for rendering a surface fly repellent, comprising applying2,3,4,5-biS(A -b11- tenylene) -tetrahydrofurfural thereto.

CAROLYN E. TISSOL. LYLE D. GOODHUE.

No references cited.

3. A METHOD FOR RENDERING A SURFACE ROACH REPELLENT, COMPRISING2,3,4,5-BIS($2-BUTENYLENE)TETRAHYDROFURFURAL THERETO.